Preparation of magnesium silicate adsorbents



' Patented Jan. 13, 1948 ES PATENT oi-Fica PREPARATION or MAGNESIUM smcn'ra sonnsnyrs William A. La Lande, In, Upper Darby, Pa., as-

' ous solution.

signor to Attapulg-ua Clay Company, Philadelphia, Pa., a corporation of Delaware Noni-swing. Application March 14, 1942 vSerial No. 434,776

8 Claims. (01. 23-110) The present invention relates to the prepara- {tion oi. adsorbent compositions, and more partic- 1 ularly to. the production of magnesium silicates or mixtures containingmagnesium silicates suitable for use as-decclorizing adsorbents and catalysts. I

An object of this invention is the preparation of adsorbent compositions by reacting in aqueous solution an alkali metal silicate and a. water-soluble salt of magnesium, in the presence of a compound'yielding ammonium ions (NI-14+) in aque- A further object of this invention is the activation of magnesium silicate adsorbents subsequent' to their formation, bytreatment with a compound yielding ammonium ions (NH4+) in aqueous solution.

It has been proposed heretofore to produce magnesium silicates by reacting an alkali metal silicate with a water-soluble salt of magnesium, or by reacting an alkali metal silicate with a water-soluble calcium salt and transposing the resulting calcium silicate to magnesium silicate by treatment with a water-solublemagnesium salt. A further method comprises the treatment of naturally-occurring caiciumsiiicates with a watersoluble salt of magnesium. A still further meth- 0d involves the treatment of magnesium basic carbonate with silica, water, and alkali at ele'- vated temperature and pressure.

However, I have discovered that by carrying out the processes aforementioned at an elevated temperature in the presence or a compound yielding NH4+ ions in aqueous solution, or by treating-the products of saidprocesses at an elevated temperature with a compound yielding 'NH4+ ions in aqueous solution, I am able to produce improvedadsorbents suitable for use as decolorizing agents or catalysts. Such silicates'difler' from those formed in the absence of compounds yieldum salt; And, finally, a naturally occurring cal-' ing NH4+ ions, in that they-possess a higher decolorizlng or bleacing' power for oils, a lower retentivity, and permit higher filtration rates when employed in the decolorization of oils, waxes, and

the like. Furthermore, the adsorbents'prepared in accordance with 'my'invention are more emcient catalysts for the conversion oi. hydrocarbons than the adsorbents produced by the prior art methods.

, In accordance with one aspect .oi invention, an alkali metal silicate is dispersed in sufllcient water to dissolvethe compound, and to this soqlution is added a second solution containing a water-soluble ammonium salt and a water-soluble salt of magnesium. While chemicaly equivalent amounts of alkali metal silicate and water-' soluble magnesium salt may be employed, I pre- The quantity of ammonimn salt may vary.v and good results have been obtained using amounts chemically equivalent to the water-soluble magnesium salt. The mixture is then heated. preterably at its boiling point, for a period of time suflicient to complete the reaction, whereby there is produced a water-insoluble product comprising magnesium'silicate. Silicates corresponding to the approximate formulae MgQSiOa,

Msozsim Mg 0.3810: and 2MgO.3SiO= may be produced.

The insoluble product is then separated from the reaction mixture by suitable means, for example, by decantation, filtering or centrifuging,

and the product is then washed free of soluble salts, dried to a suitable volatile matter content,

and reduced to particles of desired size; As alternativeprocedures, the alkali metal silicate may be reactedwith a. water-soluble magnesium salt to form a water-insoluble magnesium silicate, and the latter may then be separated-and treated at elevated temperature with a compound capable of yielding ammonium ions in aqueoussolution. or, a magnesium silicate may be prepared by reacting an alkali metal silicate with a water-soluble calcium salt, and the resulting insoluble calcium silicate then transposed into a magnesium silicate by treatment with a water-solublev magnesium salt. Or, a magnesium basic carbonate may be treated with silica, water, and alkali at elevated temperature and pressure to produce a magnesium silicate. During the formation of the silicates, a compound capable of yielding ammonium ions may advantageously be present, or the silicates, after formation, may be treated at elevated temperature with a water-soluble ammonicium silicate may be treated with a water-soluble magnesium salt, at an elevated temperature, in the presence of a compound capable of yielding ammonium ions. In general, any magnesium silicate adsorbent, either during its preparation or subsequent thereto, is improved by the presence of, or the treatment with, a compound yielding ammonium ions in aqueous solution, at temperatures above about F. Treatment of the magneslum silicate with solutions oiam'monium compounds at ordinary temperatures produces no improvement. h I

In carrying out my process, I may employ com- "mercially available alkali metal silicates having a ratio 0f.Na2O:SiO: or K2O:Si02 of 1:1 to1:4.

The silicates maybe used in aqueoussolution of desired concentration, andthe ratio of NazOfSiOz or K20:Si02 may be adjusted by the addition -of suitable quantities of NaOH or KOH. Comfer: tohave present in the reaction mixture,;an j

excess of magnesium "salt overgthat required for complete reaction with the alkali metal silicate.

.mercial sodium silicate, such as "N" brandsillcate having aratio of NaaOtSiOa oi 1:3.22, and 6 aBaum gravity of 41, has been found satisfac- 3 tory for use. Alkali metal silicates produced by the treatment of silica or other highly silicious minerals with alkali metal hydroxides, oxides. peroxides, or carbonates, may also be used. For

example, materials containing alkali metal sili-f cates produced by fusing fuller's earth, bentonite, or other naturally occurring silicates, with an alkali metal carbonate, or by treating such naturally occurring silicates with an alkali metal hydroxide solution at elevated temperatures, may be satisfactorily employed. As compounds ca-' pable of furnishing ammonium ions (NI-14+) in aqueous solution, I may utilize, for example, ammonium chloride, ammonium sulfate, or ammonium nitrate. Insofar as the water-solublemagnesium salts are concerned. I prefer to use the chloride or the sulfate, although other soluble magnesium salts may be employed. Magnesium chloride solutions, particularly magnesium chloride brines from salt wells, are available in large quantities and at relatively low cost,- and may be satisfactorily employed in the practice of my invention. While satisfactory results may be obtained using chemically equivalent amounts of an ammonium compound and of a soluble magnesium salt, based upon the alkali content of the action may be favored by having present 'an excess of the magnesium salt or the ammonium salt. The concentrations of the solutions employed may vary over a wide range, for example, from 1 per cent up to saturation at the boiling point of the solution or mixture of solutions. The temperature at which the reaction is carried out is preferably that which is necessary to maintain the solution or mixtureof the reactants 'at its boiling point, however, higher or lower temperatures may be utilized. In general, temperatures of from about 150 F. to about 400 F. are suitable, sufilcient pressure being maintained upon the reaction mixture to prevent substantial loss of water therefrom. The reaction time will vary considerably,- depending upon the quantities and concentrations of the reactants, the degree of agitation of the reaction mixture. and the temperature at which the reaction is carried out. In some cases the formation of the magnesium silicate may be completed in a few hours, whereas in other cases the reaction may require to hours, or more. The magnesium silicate, upon completion of the reaction, may be freed of soluble salts by washing with water, and then dried to a suitable volatile matter content '(water content) prior to reduction of the silicate to desired particle size. Depending upon the use to which the metal silicate is to be put, the particle size and volatile matter content will vary. The volatile content may range from 10 per cent to about 30 per cent by weight, and is preferably of the order of 15 per centper cent by weight. The particle size or mesh of the silicate may be of the order of 20-60 mesh for the percolation decolorization of oils, or 4-60 mesh for the catalytic treatment of oils or other compounds, or finer than 100 mesh for the contact decolorization of oils or-the catalytic conversion of hydrocarbons.

My invention may be further illustrated by the following examples, which, however, are not to be construed as limiting the scope-thereof:

1. 204' parts by weight of MgClzfiHeO and 107 parts by weight of NH-iClwere dissolved in 1000 parts by weight of water, and the resulting solution was introduced into a reaction ','vessel provided with a stirrer and a reflux condenser. A

. (1Na2O:3.22SiO2, 41 B6.) and 475 parts by weight of water, and this solution was added to the so- ]lution first mentioned, with vigorous stirring.

The mixture was then boiled for 2 hours at 214 It, the reflux condenser serving to prevent loss of water. As a result of the reaction between the sodium silicate and the magnesium chloride, in the presence of the ammonium chloride, there was produced a white, insoluble precipitate comprising magnesium silicate, which was filtered from the solution, washed free of solubl salts with water, and air dried. The adsorbent product so produced hada volatile content (water) of 26.2 per cent by'weight determined by heating a sample of it at 1800 F. for 20 minutes. The volume weight of the product (26.2 per cent volatile content) was 31.4 pounds per cubic foot. The decolorizing efliciency of this material was determined by contacting it with a hydrocarbon lubricating oil stock having a Saybolt Universal viscosity of seconds at 210 F., an A. P. I. gravity of 255, and an O. D. color of 821. Upon completion of the contacting step, the adsorbent was filtered from the oil andlthe color of the oil was measured. The results obtained with different quantities of the-adsorbent at diiferentte'm- 223 contacted with 15 a of adsorbent at 300 F. for 20 minutes... 245

2. A solution consisting of 1220 parts by weight of-N brand sodium silicate and 700 parts by weight of water was. added, with vigorous agitation. toa second solution consisting of 356 parts by weight of MgCl:.6H20, -562'parts by weight of NHqCl, and 1020'parts by weight of water. The mixture was boiled for 2 hours at 220 F., under a reflux condenser, until the reaction between the sodium silicate and magnesium chloride was substantially complete. The resulting water-insoluble precipitate comprising magnesium silicate was filtered from the solution, washed free of soluble salts with water, and air dried. The adsorbent so produced had a volatile content (water) of 20.9 per cent by weight, and a volume weight of 15.3 pounds per cubic foot.

The procedure above set forth was repeated,

with the exception that the NH4C1 was omitted.

The resulting product, formed in the absence of M40], had a volatile content (water) of 24.6 per cent by weight, and a volume weight of 27.7 pounds per cubic foot.

The decolorizing eiilciencies of the two products prepared as above described were determined by contacting the adsorbents with the same lubricating oil stock as employed in Example 1. The results obtained with different quantities of the adsorbents at different temperatures are as fo lows:

Adsorbent prepared in the presence of NHClz 0. D. Color Lubricating oil stock 821 contacted with 10% of adsorbent at 500 F. for 20 minutes. 272 contacted with 15% of adsorbent at 300 F. for 20 minutes.. 208 Adsorbent prepared in the absence of NHC]: Y

contacted with 107 of adsorbent at 500 F. for 20 minutes" 311 contacted with 15 o of adsorbent at 300 F. for--20 minutes" 344 3. parts by weight of Polkville bentonite (volatile content 17.2 per cent) wasthoroughly admixed with. 338 parts by weight of soda ash (NazCOs containing 10 per cent by weight of water). The mixture was dried at 220 F. to remove water, and thereafter was fused at a temperature of about 1800" F. for 3 hours. The fused .NH4Cl, and 400 parts by weight of water.

silicate mixtures at assure to pass 200mesh.

' denser. A second solution was made up consist- 200 parts by weight of'theiinely divided material from the fusionwas mixed with 500 parts by weight of water to form a slurry. To this slurry was added a solution consisting of 268 parts by weight of MgCl2.6HaO, 142 parts by weight of The mixture was then boiled. under a reflux condenser, for hours, with vigorous agitation. Upon completion of the heating period, the finely divided treated material comprising a mixture of water-insoluble silicates, including magnesium silicate, was filtered from the solution, thoroughly 1 washed with water to removesoluble salts. and

- then air dried. The silicate mixture so produced had a volatile content (water) of 35.2 per cent by weight, and a volume weight of 21.5 pounds per cubic foot. The decolorizing emciency of the sill-- cate mixture was determined by contacting with a lubricating oil stock having an O. D. color 850. The results obtained with diflerent quantities of the silicate mixture are as follows:

- 0. D. color Lubricating oil stock. 850 Contacted with 107 of silicate at 500 F. for 20 minutes 382 Contacted with o of silicate at 500 F. for minutes 274 4. 375 parts by weight of fuller's earth obtained from Attapulgus, Georgia, having a volatile content of 20.0 per cent by weight, was admixed with 7'77 parts by weight of soda ash (NarCOa containing 10 per cent by weight of water) The mixture was dried at 220 F. to remove water, and thereafterv was fused at a temperature of about 1700 F. for 3 hours. The fused mass was cooled, and then ground and screened to pass 200 mesh.

300 parts by weight of the finely divided mamagnesium silicate, was filtered from the solu- I tion, thoroughly washed with water to remove soluble salts, and their air dried. The silicate mixture so produced had a volatile content (water)v of 35.0 per cent by weight, and a volume weight, of 38.3 pounds per cubic foot.

The procedure above set forth was repeated,

with the exception that the NH4C1 was omitted.

The resulting silicate mixture had a volatile con- I tent (water) of 38.8 per cent, and a volumeweight of 30.2 pounds per cubic foot.

The decolorizing efliciencies of the two silicate mixtures prepared as above described were determined by contacting the silicates with a lubricating on stock having an 0. D. color of 821. The results obtained with different quantities of-the diirerent temperatures are as follows: g Silicates prepared in the presence of N11401:

Lubricating oil stock Contacted with 10% of silicate at 500 F. for 20 minutes..-- 394 Contacted with 15% of silicate at 500 F. for 20 minutes..." 282 contacted with 10% oi silicate at 300 F. for 20 minutes 454 Silicates prepared in the absence of NH4Cl- Oontactec. with 10% oi silicate at 500 1 f0! 20 minutes.- 550' Contactec; with 15% of silicate at 500 F. for 20 minutes 481' Contacted with 15% of silicate at 300 F. for 20 minutes..." 613 ing of 676 parts by weight of "N brandsodlum silicate (1NazO:3.22S10:, 41 B.) and 4'75 parts by weight of water, and this solution was added to the solution first mentioned. with vigorous stirring. The mixture was then boiled for 2 hours at 214 F., the reflux condenser serving to prevent loss of water. As a result of the reaction between the sodium silicate and the magnesium chloride, there was produced a white. insoluble precipitate comprising magnesium silicate, which was filtered from the solution. 220 parts by weight of this product-was dispersed in 1000 parts by weight of water, and a solution of 160 parts byweight of NHtNOa in 1000 parts by weight of water was added. The mixture was boiled for 2 hours with constant agitation, and the insoluble silicate was filtered from the solution, thoroughly washed with water, and dried. The magnesium silicate so produced had a volatile content (water) or 19.5

per cent by weight, determined by heating a sample of the silicateat 1800 F. for 20 minutes.

The volume weight of the silicate (19.5 per cent volatile content) was 31.3 pounds per cubic foot. The decolorizing efiiciency of the silicate was determined by contacting the silicate with a hydro-' carbon lubricating oil stock having a Saybolt Universal viscosity of 150 seconds at 210 F., an A. P. I. gravity of 25.5", and an O. D. color of 821.

Upon completion of the contacting step, the silicate was filtered from the oil and the color of the oil was measured. The results obtained with the silicate at different temperatures are as follows:

- O.D.color Lubricating oil stock- 821 Contacted with 15% of silicate at 500 F.

for 20 minutes 210 Contacted with 15% of silicate at 300 F.

for 20 minutes---... 259

The magnesium silicate initially prepared, without activation with NH4NO3. gave the following results:

0. D. color Lubricating oil stock 821' for 20 minutes 335" In order to determine the decolorizing eficiency for vegetable oil of the silicate activated with NHGNOZ! and of the silicate not activated with NH4NO3, a soda-cut linseed oil was contacted with each of the silicates at 210 F. for 15 minutes. The linseed oil was 'decolorized to 5.8 red (Ibvi:

bond, 6" column, 35 yellow), the yield from the silicate not activated with NH4NO3 being arbi-v trarily designated at 100 per. cent, Upon this,

basis, the yield of oil from'the silicate activated with NH NOa was found to be-225 per cent. a

6. '220 parts by weight of -"Magnesol, a commercial magnesium silicate produced in accordance with the disclosure of U. S. Patent 2,163,525

to Caldwell, was dispersed in 1000 parts by weight of water, and a solution of 160 parts by wei'ght'of NHsNO: in 1000 parts by weight oIwater was added. Th mixture was boiled for 2 hours with constant agitation, and the insoluble silicate was flltered from the solution,- thoroughlywashed 5. 204' parts byweight of MgClzfiHaO was diswith water, anddried. The activated .MaguesoP' ha a volatile content (water) of 21.4 per cent by weight. g x

The decolorizingfemciency forvegetableoil of the "Magnesol activated with'Nl- IeNOa, and thevesselprovided with a stirrer and a reflux con- "Magneso not activated with NH4NOa, was determined by contactingthese materials with sodacut linseed oil at 2 3'. for minutes. The linseed oil was deco orized to 5.8 red (Lovibond, 6" column, yellow), the yield from the Magneso not activated with NHANOS beingarbitrarily designated as 100 per cent. Upon this basis, the yield of oil from the Magnesol activated with NHANOI! was found to be 385 per cent.

From the above examples, it will be apparent that. in accordance with the present invention. highlyemcient decolorizing adsorbents may be prepared, and that such adsorbents are superior to those produced in the absence of a compound yielding NI-I4+ ions in aqueous solution.

While. in the preparation of the adsorbents above described, I prefer to eflect reaction of the components in aqueous solution by simply boiling the solution under a reflux condenser, I may dispense with the condenser and add water when necessary, or I may carry out the reaction under superatmospheric pressure. for example, in a reaction vessel at pressures up to several hundred pounds per square inch. The quantities and concentrations of the reaction components, as well as the reaction temperatures, may also be varied considerably from those shown in the examples.

The adsorbent compositions of the present invention may be employed not only as decolorizing agents for hydrocarbon oils, vegetable oils, waxes, and the like, but also may beutilized as catalysts in the cracking or conversion of hydrocarbon oils and gases into motor fuel; in the reforming of gasoline to increase the anti-knock value thereof; in the thermal treatment of oil distillates such as gasoline, furnace oil, and the like for the removal of gum-forming compounds and sulfur compounds; in the hydrogenation, dehydrogenation, or cyclization of hydrocarbon oils and gases; or as a supporter or promoter for other catalysts such as the metals, metal oxides, metal sulfides, and the like. In the cracking or conversion of hydrocarbon oils, the catalysts may be employed in the form of granules or pellets for fixed bed or moving bed operations, or in the form'of a finely divided powder for the fluid" catalyst processes.

The cracking of hydrocarbon oils such as petroleum gas oil or higher boiling oil in the presence of the silicate catalyst of the present invention may be carried out at temperatures between 700 F. and 1150 F., and preferably between 850 F. and 1050 F., under atmospheric or superatmospheric pressure, using flow rates, for ex ample, of from 1 to 5 volumes of oil per volume of catalyst per hour.

The reforming of gasoline stocks or heavy naphthas in the presence of the silicate catalysts to increase the anti-knock value of the gasoline or naphtha, may be performed at temperatures of the order of 900 F. to 1025 F. under atmospheric or higher pressure.

The conversion of hydrocarbon gases into motor fuel by cracking and polymerization in the presence of the silicate catalysts may be accomplished at temperatures between 950 F. and 1150 F., and at pressures up to about 3500 lbs. per square inch, while the dehydrogenation of such gases to produce olefin hydrocarbons may be effected at similar-temperatures but preferably at atmospheric or slightly superatmospheric pressures.

The removal of gum-forming and sulfur coming a volatile content of 21.6 per cent by weight I and a particle size finer than 200 mesh. The silicate was compressed into small pellets in a conventional pelleting machine, and the pellets were introduced into an externally heated reaction vessel. A petroleum gas oil, having a distillation range of 282 F. to 692 F. and an A. P. I. gravity of 93.1", was vaporized and passed at substantially atmospheric pressure through the catalyst chamber containing the magnesium silicate pellets. The reaction temperature was maintained at 891 F., and the flow rate at 1 volume of gas oil per volume of catalyst per hour. The products of the cracking operation were collected and separated by fractionation,and there was obtained 31.4 per cent by volume of 400 F. end

point gasoline, and 6.2 per cent by weight of un-' condensed gas. The cracking reaction was repeated, using magnesium silicate produced ac-' cording to the general procedure of Example 1, with the exception that the NHaCl was omitted from the method of preparation. and there was obtained 25.0 per cent by volume of 400 F. end point gasoline, and 4.5 per cent by weight of unco'ndensed gas. e

8. Finely divided magnesium silicate prepared 4 in accordance with Example 5, supra, in which NH4NO3 was employed in the activating treatment, was pelleted in a conventional pelleting machine. The catalyst pellets were introduced into an externally heated reaction vessel, and a petroleum gas oil having a distillation range of 282 F. to 692 F. and an A. P. I. gravity of 33.1 was vaporized and passed at substantially atmospheric pressure through the reaction vessel containing the catalyst pellets. The reaction temperature was maintained at 888 F., and the flowmate at 1 volume of gas oil per volume of catalyst per hour. The products of the cracking reaction were collected and separated by fractionation, and there was obtained 31.4 per cent by volume of 400 F. end point gasoline and 5.9 per cent by weight of uncondensed gas. based upon the oil initially charged. The cracking reaction was repeated, using magnesium silicate prepared in the manner set forth in Example 5,

- with the exception that the NH4NO3 treatment pounds from hydrocarbon distillates such as gas- 4 'temperatures of the order of 550 F. to 750 E,

was omitted, and there was obtained 25.0 per cent by volume of 400 F. end point gasoline, and 4.5 per cent by weight of uncondensed gas.

9. Finely divided "Magnesol", activated by treatment with NH4NO3 as described in Example 6, was pelleted in a conventionalpelleting machine, and the catalyst pellets were introduced into an externally heated reaction vessel. A petroleum gas oil having a distillation range of 282 F. to 692 F. and an A; P. I. gravity of 33.1 was vaporized and passed at substantially atmospheric pressure through the vessel containing the catalyst pellets. The reaction temperature was maintained at 883 F., and the flow rate at 1.2 volumes of gas oil per volume of catalyst per hour. The products of the cracking reaction were collected and separated by fractionation and there was obtained 29.0 per cent by volume of 400 F. end point gasoline, and 8.0% by weight of uncondensed gas, based upon the oil initially charged. The cracking reaction was repeated,

using MagnesoP' which had not been subjected to an activating treatment with NH4NOa, and

there was obtained 25.0 per cent by volume of silicate was filtered from the solution, thoroughly washed with water, and dried. The activated silicate had a volatile content (water) of 23.2 per cent by weight and a volume weight of 48.2 lbs. per cubic foot.

The .finely divided silicate, activated by,treatment with NH4NO: as described above, was pelleted in a conventional pelleting machine, and the catalyst pellets were introduced into an externally heated reaction vessel. A petroleum gas oil having a distillation range of 282 F. to 692 F. and an A. P. I. gravity of 331 was vaporized and passed at substantially atmospheric pressure through th vessel containing the catalyst pellets. The reaction temperature was maintained at 890 F., and the flow rate at 1.2 volumes of gas oil per volume of catalyst per hour. The products of the cracking reaction were collected and separated by fractionation and there was obtained 32.6 per cent by. volume of 400 F. end point gasoline, and 9.8% by weight of uncondensed gas, based upon the oil initially charged. The cracking reaction was repeated, using the initial silicate which had not been subjected to an activating treatment with NH4NOa, and there was obtained 16.5 per cent by volume of 400 F. end point gasoline, and 3.9 per cent by weight of uncondensed gas.

The adsorbent and catalyst compositions of the present invention may be regenerated or reviviiied after their decolorizing or catalytic activity has decreased through adsorption of carbonaceous materials during use, by treating such used adsorbents or catalysts with a solvent or solvent mixture capable of dissolving or displacing the undesirable carbonaceous materials. For example, the used adsorbents or catalystmay be washed with naphtha, alcohols, ketones; benzol, chlorinated hydrocarbon solvents, or mixtures thereof such as naphtha and acetone, in order to dis solve and remove adsorbed carbonaceous materials. Or, the used adsorbents or catalysts; with or without preliminary washing or steaming, may be rgenerated by heating, preferably in the presence of air, or gases containing controlled amounts of oxygen, in order to remove carbonaceous impurities.

I claim:

1. The method of producing an adsorbent composition, which comprises reacting in aqueous solution an alkali metal silicate and a water-soluble salt of magnesium, in the presence of a compound yielding NH4+ ions in aqueous solution at a temperature between 150 F. and 400 F., and

separating the insoluble magnesium silicate from said solution.

2. The method of producing an adsorbent composition, which comprises reacting in aqueous solution an alkali metal silicate and a watersoluble salt or magnesium, in the presence of a compound yielding NH4+ ions in aqueous solution at a temperature between 150 F. and 400 F., separating the insoluble magnesium silicate from said solution, washing said silicate to remove soluble salts, and drying the washed silicate.

3. The method of producing an adsorbent composition, which comprises comminglingin an aqueous medium an alkali metal silicate, a watersoluble salt of magnesium, and a compound yielding NH4+ ions in aqueous solution, heating said aqueous medium containing said reactants to a temperature between 150 F. and 400 F., and separating the resulting insoluble magnesium silicate from said aqueous medium.

4. The method of producing an adsorbent composition, which comprises commingling in an aqueous medium an alkali metal silicate. a watersoluble salt of magnesium, and a compound yielding NH4+ ions in aqueous solution, boiling the aqueous medium containing said reactants, separating the resulting insoluble magnesium silicate from the aqueous medium, washing said silicate to remove soluble salts, and drying the washed silicate.

5. The method of producing an adsorbent com-- position, which comprises reacting in aqueous solution sodium silicate and a water-soluble salt of magnesium, in the presence of a water-soluble ammonium salt at a temperature between 150 F. and 400 F., to form a water-insoluble magnesium silicate, and separating the insoluble silidate from saidsolution. I

6. The method of producing an adsorbent composition, which comprises commingling in an aqueous medium sodium silicate, magnesium chloride, and ammonium chloride, heating the aqueous medium containing said reactants to a temperature between 150 F. and 400 F., and separating the resulting insoluble magnesium silicate from said aqueous medium.

7. The method of producing an adsorbent composition, which comprises reacting in aqueous solution an alkali metal silicate and a watersoluble salt of magnesium, and treating the resulting water-insoluble magnesium silicate with a compound yielding NH4+ ions in ,aqueous solution at a temperature between F, and 400 F. 8. The method of producing a magnesium sili cate adsorbent, which comprises treating a waterinsoluble magnesium silicate with a compound yielding NH4+ ions in aqueous solution at a temperature between 150 F, and 400 F.

WILLIAM A. LA LANDE, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,515,007 Behrman Nov. 11, 1924 1,935,176 Connolly Nov. 14, 1933 2,229,353 Thomas et a1. Jan. 21, 1941 2,232,727 Peterkin et a1. Feb. 25, 1941 FOREIGN PATENTS Number Country Date 504,614 Great Britain Apr. 24, 1939 519,808 Great Britain Apr. 5, 1940 OTHER REFERENCES Jofle et al., Soil Science. vol. 40; pp. 255-268.- Pub. by Rutgers University, New Brunswick, N. J. (1935). 

